WO2020065723A1 - Suspension épaisse et procédé de polissage - Google Patents

Suspension épaisse et procédé de polissage Download PDF

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Publication number
WO2020065723A1
WO2020065723A1 PCT/JP2018/035445 JP2018035445W WO2020065723A1 WO 2020065723 A1 WO2020065723 A1 WO 2020065723A1 JP 2018035445 W JP2018035445 W JP 2018035445W WO 2020065723 A1 WO2020065723 A1 WO 2020065723A1
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WIPO (PCT)
Prior art keywords
particles
mass
slurry
polishing
less
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PCT/JP2018/035445
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English (en)
Japanese (ja)
Inventor
友洋 岩野
貴彬 松本
友美 久木田
智康 長谷川
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日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to PCT/JP2018/035445 priority Critical patent/WO2020065723A1/fr
Priority to CN201880097934.8A priority patent/CN112740366A/zh
Priority to KR1020217010330A priority patent/KR102382508B1/ko
Priority to US17/278,974 priority patent/US20220033680A1/en
Priority to JP2020547634A priority patent/JP6888744B2/ja
Publication of WO2020065723A1 publication Critical patent/WO2020065723A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1436—Composite particles, e.g. coated particles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the present invention relates to a slurry and a polishing method.
  • a CMP (Chemical Mechanical Polishing) technique which is one of the processing techniques, forms a shallow trench isolation (shallow trench isolation; hereinafter, referred to as "STI") in a semiconductor device manufacturing process. It is an indispensable technique for flattening a premetal insulating material or an interlayer insulating material, forming a plug or a buried metal wiring, and the like.
  • the most frequently used polishing liquid is, for example, a silica-based polishing liquid containing silica (silicon oxide) particles such as fumed silica and colloidal silica as abrasive grains.
  • the silica-based polishing liquid is characterized by being highly versatile, and can appropriately polish a wide variety of materials irrespective of insulating materials and conductive materials by appropriately selecting the abrasive content, pH, additives, and the like.
  • a polishing liquid mainly for an insulating material such as silicon oxide the demand for a polishing liquid containing cerium compound particles as abrasive grains is also increasing.
  • a cerium oxide-based polishing liquid containing cerium oxide particles as abrasive grains can polish silicon oxide at high speed even with a lower abrasive content than a silica-based polishing liquid (for example, see Patent Documents 1 and 2 below).
  • the step of the insulating material at the time of forming the cell is several times higher than that of the conventional planar type. Accordingly, in order to maintain the device manufacturing throughput, it is necessary to quickly eliminate the high steps as described above in the CMP process or the like, and it is necessary to improve the polishing rate of the insulating material.
  • silicon oxide containing carbon may be used as an insulating material. Therefore, even when silicon oxide containing carbon is used, it is required to improve the polishing rate of silicon oxide containing carbon from the viewpoint of quickly eliminating the above-described steps.
  • the present invention has been made to solve the above problems, and has as its object to provide a slurry capable of improving the polishing rate of silicon oxide containing carbon, and a polishing method using the slurry.
  • a slurry according to one aspect of the present invention is a slurry for polishing silicon oxide containing carbon, which includes abrasive grains and a liquid medium, wherein the abrasive grains include first particles and the second particles.
  • the polishing rate of silicon oxide containing carbon can be improved, and silicon oxide containing carbon can be polished at a high polishing rate.
  • a polishing method includes a step of polishing a surface to be polished using the slurry. According to such a polishing method, the same effect as that of the slurry can be obtained by using the slurry.
  • a slurry capable of improving the polishing rate of silicon oxide containing carbon can be provided.
  • a polishing method using the slurry can be provided.
  • the use of the slurry for polishing silicon oxide containing carbon can be provided. According to the present invention, it is possible to provide the use of the slurry in the step of flattening the surface of the substrate, which is a technique for manufacturing a semiconductor device. According to the present invention, it is possible to provide the use of the slurry in the step of planarizing an STI insulating material, a pre-metal insulating material or an interlayer insulating material.
  • a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively.
  • the upper limit or the lower limit of a numerical range in one step can be arbitrarily combined with the upper limit or the lower limit of a numerical range in another step.
  • the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment.
  • “A or B” may include one of A and B, and may include both.
  • the materials exemplified in the present specification can be used alone or in combination of two or more, unless otherwise specified.
  • the content of each component in the composition if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition Means
  • step is included in the term as well as an independent step, even if it is not clearly distinguishable from other steps, provided that the intended action of that step is achieved.
  • the slurry according to the present embodiment contains abrasive grains.
  • the abrasive grains are also referred to as “abrasive particles”, but are referred to herein as “abrasive grains”.
  • Abrasive grains are generally solid particles, and are removed by a mechanical action (physical action) of the abrasive grains during polishing and a chemical action of the abrasive grains (mainly, the surface of the abrasive grains). It is contemplated, but not limited to, that the object is removed.
  • the polishing rate when the slurry according to the present embodiment is used is, for example, the polishing rate obtained when the content of abrasive grains (total amount of particles) is adjusted to 0.1% by mass based on the total mass of the slurry. Can be compared based on
  • the weight average molecular weight in the present specification can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve under the following conditions.
  • Equipment used Hitachi L-6000 type [manufactured by Hitachi, Ltd.]
  • Flow rate 1.75 mL / min
  • Detector L-3300RI [manufactured by Hitachi, Ltd.]
  • the slurry according to the present embodiment is a slurry for polishing silicon oxide containing carbon.
  • Examples of the silicon oxide containing carbon include black diamond.
  • the slurry according to the present embodiment contains abrasive grains and a liquid medium as essential components.
  • the slurry according to the present embodiment can be used, for example, as a polishing liquid (CMP polishing liquid).
  • polishing liquid abrasive
  • polishing liquid is defined as a composition that comes into contact with a surface to be polished during polishing.
  • the phrase "polishing liquid” itself does not limit the components contained in the polishing liquid at all.
  • Abrasive grains contain composite particles including first particles and second particles in contact with the first particles.
  • the particle size of the second particles is smaller than the particle size of the first particles.
  • the first particles contain a cerium oxide and the second particles contain a cerium compound.
  • the polishing rate of silicon oxide containing carbon can be improved.
  • the reasons why the polishing rate is improved as described above include, for example, the following reasons. However, the reason is not limited to the following.
  • the first particles containing cerium oxide and having a particle size larger than the second particles have a mechanical action (mechanical properties) on silicon oxide containing carbon as compared with the second particles. strong.
  • the second particles containing the cerium compound and having a smaller particle size than the first particles have a smaller mechanical action on silicon oxide containing carbon as compared with the first particles, but have a smaller particle size.
  • a synergistic effect of improving the polishing rate is easily obtained.
  • silicon oxide containing carbon hydrophobicity tends to be stronger as compared with the case where carbon is not contained.
  • the affinity of silicon oxide for a slurry containing a liquid medium such as water tends to be low, and the use of conventional particles tends to lower the polishing rate.
  • the above-described composite particles are used for polishing, so that a sufficient polishing effect can be obtained even on a material to be polished (silicon oxide containing carbon) having relatively low affinity. Is exhibited. From the above, it is inferred that the polishing rate of silicon oxide containing carbon can be improved by using the slurry according to the present embodiment.
  • the abrasive grains of the slurry according to the present embodiment include the composite particles including the first particles and the second particles in contact with the first particles.
  • the particle size of the second particles is smaller than the particle size of the first particles.
  • the magnitude relationship between the particle diameters of the first particles and the second particles can be determined from an SEM image or the like of the composite particles.
  • the lower limit of the particle size of the first particles is preferably 15 nm or more, more preferably 25 nm or more, still more preferably 35 nm or more, particularly preferably 40 nm or more, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. Above is extremely preferred, 80 nm or more is very preferred, and 100 nm or more is even more preferred.
  • the upper limit of the particle diameter of the first particles is preferably 1,000 nm or less, more preferably 800 nm or less, and 600 nm or less, from the viewpoint of improving the dispersibility of the abrasive grains, and from the viewpoint that scratches on the surface to be polished are easily suppressed.
  • the particle diameter of the first particles is more preferably 15 to 1000 nm.
  • the average particle size (average secondary particle size) of the first particles may be in the above range.
  • the lower limit of the particle size of the second particles is preferably 1 nm or more, more preferably 2 nm or more, and still more preferably 3 nm or more, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon.
  • the upper limit of the particle size of the second particles is preferably 50 nm or less, more preferably 30 nm or less, and 25 nm from the viewpoint that the dispersibility of the abrasive grains is improved and that the surface to be polished is easily suppressed from being damaged.
  • the thickness is particularly preferably 20 nm or less, particularly preferably 15 nm or less, and very preferably 10 nm or less. From the above viewpoint, the particle size of the second particles is more preferably 1 to 50 nm.
  • the average particle size (average secondary particle size) of the second particles may be in the above range.
  • the average particle size (average secondary particle size) of the abrasive grains (the entire abrasive grains such as composite particles) in the slurry is preferably in the following range.
  • the lower limit of the average particle size of the abrasive grains is preferably 16 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, particularly preferably 40 nm or more, and particularly preferably 50 nm or more, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. Is very preferably, 100 nm or more is very preferable, 120 nm or more is still more preferable, and 140 nm or more is still more preferable.
  • the upper limit of the average particle size of the abrasive grains is preferably 1050 nm or less, more preferably 1000 nm or less, and 800 nm or less, from the viewpoint of improving the dispersibility of the abrasive grains and from the viewpoint that the surface to be polished is easily suppressed from being damaged.
  • the average particle diameter of the abrasive grains is more preferably 16 to 1050 nm.
  • the average particle size is measured using, for example, a light diffraction scattering type particle size distribution meter (for example, trade name: N5, manufactured by Beckman Coulter, Inc., or Microtrac Bell, Inc., trade name: Microtrac MT3300EXII). can do.
  • a light diffraction scattering type particle size distribution meter for example, trade name: N5, manufactured by Beckman Coulter, Inc., or Microtrac Bell, Inc., trade name: Microtrac MT3300EXII.
  • the first particles contain a cerium oxide (eg, ceria), and the second particles contain a cerium compound.
  • the cerium compound of the second particles include cerium hydroxide and cerium oxide.
  • cerium compound of the second particles a compound different from cerium oxide can be used.
  • the cerium compound preferably contains cerium hydroxide. Abrasive grains containing cerium hydroxide have a higher reactivity (chemical action) with silicon oxide containing carbon due to the action of a hydroxyl group than particles made of silica, cerium oxide, and the like. Silicon can be polished at a higher polishing rate.
  • Cerium hydroxide is, for example, a compound containing tetravalent cerium (Ce 4+ ) and at least one hydroxide ion (OH ⁇ ).
  • Cerium hydroxide may include anions other than hydroxide ions (eg, nitrate ions NO 3 ⁇ and sulfate ions SO 4 2 ⁇ ).
  • cerium hydroxide may include anions (eg, nitrate NO 3 ⁇ and sulfate SO 4 2 ⁇ ) bound to tetravalent cerium.
  • Cerium hydroxide can be produced by reacting a cerium salt with an alkali source (base).
  • the cerium hydroxide is preferably produced by mixing a cerium salt and an alkaline liquid (for example, an alkaline aqueous solution).
  • an alkaline liquid for example, an alkaline aqueous solution.
  • Cerium hydroxide can be obtained by mixing a cerium salt solution (for example, a cerium salt aqueous solution) and an alkali solution.
  • cerium salt conventionally known ones can be used without particular limitation, and Ce (NO 3 ) 4 , Ce (SO 4 ) 2 , Ce (NH 4 ) 2 (NO 3 ) 6 , Ce (NH 4 ) 4 (SO 4 ) 4 and the like.
  • the composite particles including the first particles and the second particles are brought into contact with the first particles and the second particles using a homogenizer, a nanomizer, a ball mill, a bead mill, an ultrasonic treatment machine, or the like, and the charges opposite to each other are used.
  • a homogenizer a nanomizer, a ball mill, a bead mill, an ultrasonic treatment machine, or the like.
  • the lower limit of the content of the cerium oxide in the first particles is that the whole of the first particles (the whole of the first particles contained in the slurry; hereinafter the same) from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. ), 50% by mass or more is preferable, 70% by mass or more is more preferable, 90% by mass or more is more preferable, and 95% by mass or more is particularly preferable.
  • the first particles may be in an aspect substantially composed of cerium oxide (an aspect in which 100% by mass of the first particles is cerium oxide).
  • the lower limit of the content of the cerium compound in the second particles is that the whole of the second particles (the whole of the second particles contained in the slurry; the same applies hereinafter) from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. Is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on
  • the second particles may have an aspect substantially composed of a cerium compound (an aspect in which substantially 100% by mass of the second particles is a cerium compound).
  • the lower limit of the content of the first particles in the abrasive grains is 50 mass% based on the entire abrasive grains (the entire abrasive grains contained in the slurry; the same applies hereinafter) from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. % Or more, more preferably more than 50% by mass, still more preferably 60% by mass or more, particularly preferably 70% by mass or more, and very preferably 75% by mass or more.
  • the upper limit of the content of the first particles in the abrasive grains is preferably 95% by mass or less, more preferably 93% by mass or less, based on the entire abrasive particles, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon.
  • the content of the first particles in the abrasive grains is more preferably 50 to 95% by mass based on the entire abrasive grains.
  • the lower limit of the content of the second particles in the abrasive grains is 5% by mass or more based on the entire abrasive grains (the entire abrasive grains contained in the slurry) from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. It is preferably 7% by mass or more, more preferably 10% by mass or more, particularly preferably 12% by mass or more, particularly preferably 14% by mass or more, very preferably 15% by mass or more, and still more preferably 18% by mass or more. It is preferably at least 20% by mass, more preferably at least 22% by mass.
  • the upper limit of the content of the second particles in the abrasive grains is preferably 50% by mass or less, more preferably less than 50% by mass, based on the entire abrasive particles, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. , 40% by mass or less is more preferable, 30% by mass or less is particularly preferable, and 25% by mass or less is very preferable. From the above viewpoint, the content of the second particles in the abrasive grains is more preferably 5 to 50% by mass based on the entire abrasive grains.
  • the lower limit of the content of cerium oxide in the abrasive grains is preferably 50% by mass or more based on the entire abrasive grains (the entire abrasive grains contained in the slurry) from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. , More preferably more than 50% by mass, still more preferably 60% by mass or more, particularly preferably 70% by mass or more, and very preferably 75% by mass or more.
  • the upper limit of the content of cerium oxide in the abrasive grains is preferably 95% by mass or less, more preferably 93% by mass or less, based on the entire abrasive grain, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon.
  • the content of cerium oxide in the abrasive grains is more preferably 50 to 95% by mass based on the entire abrasive grains.
  • the lower limit of the content of cerium hydroxide in the abrasive grains is 5% by mass or more based on the entire abrasive grains (the entire abrasive grains contained in the slurry) from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. It is preferably 7% by mass or more, more preferably 10% by mass or more, particularly preferably 12% by mass or more, particularly preferably 14% by mass or more, very preferably 15% by mass or more, and still more preferably 18% by mass or more. It is preferably at least 20% by mass, more preferably at least 22% by mass.
  • the upper limit of the content of cerium hydroxide in the abrasive grains is preferably 50% by mass or less, more preferably less than 50% by mass, based on the entire abrasive grain, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. , 40% by mass or less is more preferable, 30% by mass or less is particularly preferable, and 25% by mass or less is very preferable. From the above viewpoint, the content of cerium hydroxide in the abrasive grains is more preferably 5 to 50% by mass based on the entire abrasive grains.
  • the lower limit of the content of the first particles is preferably 50% by mass or more based on the total amount of the first particles and the second particles, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. It is more preferably more than 70% by mass, more preferably 60% by mass or more, particularly preferably 70% by mass or more, and very preferably 75% by mass or more.
  • the upper limit of the content of the first particles is preferably 95% by mass or less, based on the total amount of the first particles and the second particles, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. 80% by mass or less, particularly preferably 88% by mass or less, particularly preferably 86% by mass or less, very preferably 85% by mass or less, even more preferably 82% by mass or less. It is more preferably at most 78 mass%, particularly preferably at most 78 mass%. From the above viewpoint, the content of the first particles is more preferably 50 to 95% by mass based on the total amount of the first particles and the second particles.
  • the lower limit of the content of the second particles is preferably 5% by mass or more, based on the total amount of the first particles and the second particles, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. Is preferably at least 10% by mass, more preferably at least 12% by mass, particularly preferably at least 14% by mass, very preferably at least 15% by mass, even more preferably at least 18% by mass. It is more preferably at least 22 mass%, particularly preferably at least 22 mass%.
  • the upper limit of the content of the second particles is preferably 50% by mass or less, based on the total amount of the first particles and the second particles, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon.
  • the content of the second particles is more preferably 5 to 50% by mass based on the total amount of the first particles and the second particles.
  • the lower limit of the content of the first particles in the slurry is preferably 0.005% by mass or more, more preferably 0.008% by mass, based on the total mass of the slurry, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon.
  • the above is more preferable, 0.01% by mass or more is further preferable, 0.03% by mass or more is particularly preferable, 0.05% by mass or more is very preferable, and 0.07% by mass or more is very preferable.
  • the upper limit of the content of the first particles in the slurry is 5 mass% based on the total mass of the slurry, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon and increasing the storage stability of the slurry.
  • the content of the first particles in the slurry is more preferably 0.005 to 5% by mass based on the total mass of the slurry.
  • the lower limit of the content of the second particles in the slurry is such that the chemical interaction between the abrasive grains and the surface to be polished is further improved, and the polishing rate of silicon oxide containing carbon is further improved.
  • 0.005 mass% or more is preferable, 0.008 mass% or more is more preferable, 0.01 mass% or more is more preferable, 0.012 mass% or more is especially preferable, and 0.015 mass% or more is based on mass. Is very preferably 0.018% by mass or more, very preferably 0.02% by mass or more, further preferably 0.0225% by mass or more, and particularly preferably 0.023% by mass or more.
  • the upper limit of the content of the second particles in the slurry makes it easier to avoid agglomeration of the abrasive grains, further enhances the chemical interaction between the abrasive grains and the surface to be polished, and improves the properties of the abrasive grains.
  • the amount is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, based on the total mass of the slurry.
  • the content is very preferably 1% by mass or less, very preferably 0.05% by mass or less, further preferably 0.04% by mass or less, still more preferably 0.035% by mass or less, and still more preferably 0.03% by mass or less.
  • the content of the second particles in the slurry is more preferably 0.005 to 5% by mass based on the total mass of the slurry.
  • the lower limit of the content of cerium oxide in the slurry is preferably 0.005% by mass or more, more preferably 0.008% by mass or more based on the total mass of the slurry, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. Is more preferably 0.01% by mass or more, further preferably 0.03% by mass or more, particularly preferably 0.05% by mass or more, and very preferably 0.07% by mass or more.
  • the upper limit of the content of cerium oxide in the slurry is 5% by mass based on the total mass of the slurry, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon and increasing the storage stability of the slurry.
  • the content of cerium oxide in the slurry is more preferably 0.005 to 5% by mass based on the total mass of the slurry.
  • the lower limit of the cerium hydroxide content in the slurry is such that the chemical interaction between the abrasive grains and the surface to be polished is further improved, and the polishing rate of silicon oxide containing carbon is further improved.
  • 0.005 mass% or more is preferable, 0.008 mass% or more is more preferable, 0.01 mass% or more is more preferable, 0.012 mass% or more is especially preferable, and 0.015 mass% or more is based on mass. Is very preferably 0.018% by mass or more, very preferably 0.02% by mass or more, further preferably 0.0225% by mass or more, and particularly preferably 0.023% by mass or more.
  • the upper limit of the content of cerium hydroxide in the slurry makes it easier to avoid agglomeration of the abrasive grains, and further enhances the chemical interaction between the abrasive grains and the surface to be polished, thereby improving the properties of the abrasive grains.
  • the amount is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, based on the total mass of the slurry.
  • the content is very preferably 1% by mass or less, very preferably 0.05% by mass or less, further preferably 0.04% by mass or less, still more preferably 0.035% by mass or less, and still more preferably 0.03% by mass or less.
  • the content of the cerium hydroxide in the slurry is more preferably 0.005 to 5% by mass based on the total mass of the slurry.
  • the lower limit of the content of the abrasive grains in the slurry is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more based on the total mass of the slurry, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. More preferably, the content is more preferably 0.09% by mass or more.
  • the upper limit of the content of the abrasive grains in the slurry is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the slurry, from the viewpoint of increasing the storage stability of the slurry.
  • the content is more preferably 0.5% by mass or less, particularly preferably 0.1% by mass or less. From the above viewpoint, the content of the abrasive grains in the slurry is more preferably 0.01 to 10% by mass based on the total mass of the slurry.
  • the first particles can have a negative zeta potential.
  • the second particles can have a positive zeta potential.
  • the zeta potential indicates the surface potential of the particles.
  • the zeta potential can be measured using, for example, a dynamic light scattering zeta potential measuring device (for example, trade name: DelsaNano @ C, manufactured by Beckman Coulter, Inc.).
  • the zeta potential of the particles can be adjusted using additives. For example, by bringing a monocarboxylic acid (for example, acetic acid) into contact with particles containing cerium oxide, particles having a positive zeta potential can be obtained. Further, particles having a negative zeta potential can be obtained by bringing ammonium dihydrogen phosphate, a material having a carboxyl group (eg, polyacrylic acid) or the like into contact with particles containing cerium oxide.
  • the second particles contain cerium hydroxide and satisfy at least one of the following conditions (a) and (b).
  • the “aqueous dispersion” in which the content of the second particles is adjusted to a predetermined amount means a liquid containing a predetermined amount of the second particles and water.
  • the second particles give an absorbance of 1.00 or more to light having a wavelength of 400 nm in an aqueous dispersion in which the content of the second particles is adjusted to 1.0% by mass.
  • the second particles give an absorbance of 1.000 or more to light having a wavelength of 290 nm in an aqueous dispersion in which the content of the second particles is adjusted to 0.0065% by mass.
  • the polishing rate is further improved by using particles that give an absorbance of 1.00 or more for light having a wavelength of 400 nm in an aqueous dispersion in which the content of the second particles is adjusted to 1.0% by mass. Can be done.
  • the reason for this is not necessarily clear, but the present inventor thinks as follows. That is, it is composed of tetravalent cerium (Ce 4+ ), one to three hydroxide ions (OH ⁇ ), and one to three anions (X c ⁇ ), depending on the production conditions of the cerium hydroxide.
  • the particles containing cerium hydroxide may include not only Ce (OH) a Xb but also Ce (OH) 4 , CeO 2 and the like.
  • Examples of the anion (X c ⁇ ) include NO 3 — and SO 4 2- .
  • the fact that the particles containing cerium hydroxide contain Ce (OH) a Xb is based on the fact that the particles are thoroughly washed with pure water and then the FT-IR ATR method (Fourier transform Infra Red Spectrometer Attenuated Total Reflection method, Fourier transform) It can be confirmed by a method of detecting a peak corresponding to an anion (X c ⁇ ) by infrared spectrophotometry total reflection measurement. The presence of an anion (X c ⁇ ) can also be confirmed by XPS (X-ray Photoelectron Spectroscopy, X-ray photoelectron spectroscopy).
  • the absorption peak of Ce (OH) a Xb (for example, Ce (OH) 3 X) at a wavelength of 400 nm is much smaller than the absorption peak at a wavelength of 290 nm described later.
  • the present inventor examined the magnitude of the absorbance using an aqueous dispersion having a content of 1.0% by mass, in which the content of the particles was relatively large and the absorbance was large and easily detected. It has been found that the use of particles that give an absorbance of at least 1.00 for light having a wavelength of 400 nm in the liquid is excellent in improving the polishing rate.
  • the lower limit of the absorbance with respect to light having a wavelength of 400 nm is preferably 1.50 or more, more preferably 1.55 or more, and still more preferably 1.60 or more, from the viewpoint of making it easier to polish silicon oxide containing carbon at a more excellent polishing rate. preferable.
  • the polishing rate can be increased by using the second particles that give an absorbance of 1.000 or more to light having a wavelength of 290 nm in an aqueous dispersion in which the content of the second particles is adjusted to 0.0065% by mass. Can be further improved.
  • the present inventor thinks as follows. That is, particles containing Ce (OH) a Xb (for example, Ce (OH) 3 X) generated according to the production conditions of cerium hydroxide have an absorption peak near a wavelength of 290 nm in calculation, For example, particles composed of Ce 4+ (OH ⁇ ) 3 NO 3 ⁇ have an absorption peak at a wavelength of 290 nm. Therefore, it is considered that the polishing rate is improved as the abundance of Ce (OH) a Xb increases and the absorbance with respect to light having a wavelength of 290 nm increases.
  • the absorbance with respect to light having a wavelength of about 290 nm tends to be detected so as to exceed the measurement limit.
  • the present inventor examined the magnitude of the absorbance using an aqueous dispersion having a content of 0.0065% by mass, in which the content of the particles was relatively small, the absorbance was small, and the absorbance was small. It has been found that, when particles that give an absorbance of 1.000 or more to light having a wavelength of 290 nm are used in the liquid, the polishing rate is effectively improved.
  • the lower limit of the absorbance to light having a wavelength of 290 nm is more preferably 1.050 or more, still more preferably 1.100 or more, and particularly preferably 1.130 or more, from the viewpoint of polishing silicon oxide containing carbon at a more excellent polishing rate. , 1.150 or more is very preferable.
  • the upper limit of the absorbance for light having a wavelength of 290 nm is not particularly limited, but is preferably, for example, 10.00 or less.
  • the second particles that give an absorbance of 1.00 or more to light having a wavelength of 400 nm are in an aqueous dispersion in which the content of the second particles has been adjusted to 0.0065% by mass, and have an absorbance of 1.000 or more to light having a wavelength of 290 nm.
  • Silicon oxide containing carbon can be polished at an even higher polishing rate.
  • cerium hydroxide for example, Ce (OH) a Xb
  • Ce (OH) a Xb a Xb
  • the second particles contain the second particles. It is preferable that the aqueous dispersion adjusted to the amount of 0.0065 mass% (65 ppm) gives an absorbance of 0.010 or less with respect to light having a wavelength of 450 to 600 nm.
  • the absorbance for all light in the wavelength range of 450 to 600 nm does not exceed 0.010 in the aqueous dispersion in which the content of the second particles is adjusted to 0.0065% by mass.
  • the upper limit of the absorbance for light having a wavelength of 450 to 600 nm is more preferably less than 0.010.
  • the lower limit of the absorbance for light having a wavelength of 450 to 600 nm is preferably 0.
  • the absorbance of the aqueous dispersion can be measured using, for example, a spectrophotometer (device name: U3310) manufactured by Hitachi, Ltd. Specifically, for example, an aqueous dispersion in which the content of the second particles is adjusted to 1.0% by mass or 0.0065% by mass is prepared as a measurement sample. About 4 mL of this measurement sample is placed in a 1 cm square cell, and the cell is placed in the apparatus. Next, absorbance is measured in the wavelength range of 200 to 600 nm, and the absorbance is determined from the obtained chart.
  • a spectrophotometer device name: U3310
  • an aqueous dispersion in which the content of the second particles is adjusted to 1.0% by mass or 0.0065% by mass is prepared as a measurement sample. About 4 mL of this measurement sample is placed in a 1 cm square cell, and the cell is placed in the apparatus. Next, absorbance is measured in the wavelength range of 200 to 600 nm, and the absorbance is determined from the obtained chart.
  • the second particles contained in the slurry according to the present embodiment have a light transmittance of 50% / cm with respect to light having a wavelength of 500 nm in an aqueous dispersion in which the content of the second particles is adjusted to 1.0% by mass. It is preferable to provide the above. As a result, a decrease in the polishing rate due to the addition of the additive can be further suppressed, so that it is easy to obtain other characteristics while maintaining the polishing rate.
  • the lower limit of the light transmittance is more preferably 60% / cm or more, still more preferably 70% / cm or more, particularly preferably 80% / cm or more, particularly preferably 90% / cm or more, and 92% or more. / Cm or more is very preferable.
  • the upper limit of the light transmittance is 100% / cm.
  • particles present in the aqueous dispersion are relatively large particles (hereinafter, referred to as “coarse particles”). It is thought that there are many.
  • an additive for example, polyvinyl alcohol (PVA)
  • PVA polyvinyl alcohol
  • the particles present in the aqueous dispersion have a small number of “coarse particles”.
  • an additive for example, polyvinyl alcohol
  • the number of the coarse particles serving as the nucleus of the aggregation is small, so that the aggregation of the particles can be suppressed, Alternatively, the size of the aggregated particles decreases.
  • the number of particles (effective number of particles) acting on the surface to be polished per unit area is maintained, and the specific surface area of the particles in contact with the surface to be polished is maintained. .
  • the slurry is visually transparent (having a high light transmittance) and visually turbid ( It has been found that some of them have low light transmittance. From this, it is thought that even a very small amount of the coarse particles which can cause the above-mentioned action can not be detected by a general particle size measuring device, contributes to the reduction of the polishing rate.
  • the present inventor has found that the above problem can be solved by using particles having a high light transmittance in the aqueous dispersion by devising a method for producing the particles.
  • the light transmittance can be measured with a spectrophotometer. Specifically, for example, it can be measured with a spectrophotometer U3310 manufactured by Hitachi, Ltd.
  • an aqueous dispersion in which the content of the second particles is adjusted to 1.0% by mass is prepared as a measurement sample. Approximately 4 mL of this measurement sample is placed in a 1 cm square cell, and the cell is set in the apparatus before measurement.
  • the absorbance and light transmittance given to the aqueous dispersion by the second particles contained in the slurry are such that after removing solid components other than the second particles and liquid components other than water, the aqueous dispersion having a predetermined content is removed.
  • the solid component or the liquid component can be removed, for example, by centrifugation using a centrifugal machine capable of applying a gravitational acceleration of several thousand G or less, or a gravitational acceleration of tens of thousands G or more.
  • Centrifugation methods such as ultracentrifugation using an ultracentrifuge; chromatography methods such as partition chromatography, adsorption chromatography, gel permeation chromatography, and ion exchange chromatography; natural filtration, vacuum filtration, pressure filtration, and ultrafiltration Filtration methods such as filtration; distillation methods such as distillation under reduced pressure and atmospheric pressure can be used, and these may be appropriately combined.
  • the method of separating the second particles includes a chromatography method, a filtration method, and the like. At least one selected from the group consisting of ultrafiltration is preferred.
  • a filtration method is used, particles contained in the slurry can be passed through a filter by setting appropriate conditions.
  • examples of the method for separating the second particles include a chromatography method, a filtration method, and a distillation method.
  • the method for separating the second particles includes a filtration method and a centrifugal separation method.
  • the filtrate is used, and in the case of centrifugation, the liquid phase is used.
  • the liquid phase is used.
  • separation can be performed under the following centrifugation conditions.
  • Centrifuge Optima MAX-TL (manufactured by Beckman Coulter, Inc.) Centrifugal acceleration: 5.8 ⁇ 10 4 G Processing time: 5 minutes Processing temperature: 25 ° C
  • the second particles can be separated and / or other components can be separated under the following conditions.
  • Sample solution 100 ⁇ L of slurry Detector: UV-VIS detector, manufactured by Hitachi, Ltd., trade name "L-4200" Wavelength: 400nm Integrator: GPC integrator manufactured by Hitachi, Ltd., product name "D-2500” Pump: Hitachi Ltd.
  • the second particles cannot be fractionated even under the above conditions, but in that case, the sample solution amount, column type, eluent type, measurement temperature, flow rate, etc. are optimized. Can be separated. Further, by adjusting the pH of the slurry, there is a possibility that the distillation time of the components contained in the slurry is adjusted and the slurry can be separated from the second particles. When there is an insoluble component in the slurry, it is preferable to remove the insoluble component by filtration, centrifugation or the like as necessary.
  • the slurry according to the present embodiment may contain particles other than the composite particles including the first particles and the second particles.
  • particles for example, the first particles not in contact with the second particles; the second particles not in contact with the first particles; silica, alumina, zirconia, yttria And the like (particles not containing the first particles and the second particles).
  • the liquid medium is not particularly limited, but water such as deionized water and ultrapure water is preferable.
  • the content of the liquid medium may be the remainder of the slurry excluding the content of other components, and is not particularly limited.
  • the slurry according to the present embodiment may further contain an optional additive.
  • the optional additive include a material having a carboxyl group (excluding a compound corresponding to a polyoxyalkylene compound or a water-soluble polymer), a polyoxyalkylene compound, a water-soluble polymer, an oxidizing agent (for example, hydrogen peroxide), and a dispersion.
  • Agents for example, phosphoric acid-based inorganic salts.
  • Each of the additives can be used alone or in combination of two or more.
  • Examples of the material having a carboxyl group include monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and valeric acid; hydroxy acids such as lactic acid, malic acid, and citric acid; and dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, and maleic acid.
  • Monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and valeric acid
  • hydroxy acids such as lactic acid, malic acid, and citric acid
  • dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, and maleic acid.
  • Polycarboxylic acids such as polyacrylic acid and polymaleic acid
  • amino acids such as arginine, histidine and lysine.
  • Polyoxyalkylene compounds include polyalkylene glycols, polyoxyalkylene derivatives and the like.
  • polyalkylene glycol examples include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like.
  • polyalkylene glycol at least one selected from the group consisting of polyethylene glycol and polypropylene glycol is preferable, and polyethylene glycol is more preferable.
  • the polyoxyalkylene derivative is, for example, a compound obtained by introducing a functional group or a substituent into polyalkylene glycol, or a compound obtained by adding a polyalkylene oxide to an organic compound.
  • the functional group or the substituent include an alkyl ether group, an alkyl phenyl ether group, a phenyl ether group, a styrenated phenyl ether group, a glyceryl ether group, an alkylamine group, a fatty acid ester group, and a glycol ester group.
  • polyoxyalkylene derivative examples include polyoxyethylene alkyl ether, polyoxyethylene bisphenol ether (for example, BA glycol series manufactured by Nippon Emulsifier Co., Ltd.), and polyoxyethylene styrenated phenyl ether (for example, Emulgen manufactured by Kao Corporation) Series), polyoxyethylene alkylphenyl ether (eg, Neugen EA series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyalkylene polyglyceryl ether (eg, SC-E series and SC-P series manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) Polyoxyethylene sorbitan fatty acid ester (for example, Daiichi Kogyo Seiyaku Co., Ltd., Sorgen TW series), polyoxyethylene fatty acid ester (for example, Kao Corporation, Emanon series), Lioxyethylene alkylamine (for example, Amiradin D, manufactured by Daiichi Kogyo Seiyaku
  • Water-soluble polymer is defined as a polymer that is soluble in 0.1 g or more in 100 g of water.
  • the polymer corresponding to the polyoxyalkylene compound is not included in the “water-soluble polymer”.
  • acrylic polymers such as polyacrylamide and polydimethylacrylamide; polysaccharides such as carboxymethylcellulose, agar, curdlan, dextrin, cyclodextrin, and pullulan; polyvinyl alcohol, polyvinylpyrrolidone, and polysaccharide Vinyl-based polymers such as acrolein; glycerin-based polymers such as polyglycerin and polyglycerin derivatives; and polyethylene glycol.
  • the absorbance for light at 380 nm exceeds zero. In this case, the polishing rate of silicon oxide containing carbon can be further improved.
  • the reasons why the polishing rate is improved as described above include, for example, the following reasons.
  • the reason is not limited to the following. That is, if the absorbance of the liquid phase obtained when the slurry is centrifuged at a wavelength of 380 nm exceeds 0, the composite particles are easily removed selectively by such centrifugation, and the separated particles (hereinafter, referred to as “ For example, it is possible to obtain a liquid phase containing, as a solid component, a second particle which is not in contact with the first particle), and if the absorbance exceeds 0, the abrasive grains are not dispersed in the slurry. Free particles (eg, second particles that are not in contact with the first particles) are included in addition to the composite particles.
  • the free particles have a smaller particle size than the composite particles, the diffusion speed in the slurry is high, and the free particles are preferentially adsorbed on the surface of silicon oxide containing carbon to cover the surface.
  • the composite particles act not only directly on the carbon-containing silicon oxide, but also on the free particles adsorbed on the carbon-containing silicon oxide, and indirectly act on the carbon-containing silicon oxide. (Eg, mechanical action can be transferred to carbon-containing silicon oxide via free particles adsorbed on the carbon-containing silicon oxide).
  • the absorbance for light having a wavelength of 380 nm in a liquid phase obtained when the slurry according to the present embodiment is centrifuged at a centrifugal acceleration of 5.8 ⁇ 10 4 G for 5 minutes is preferably in the following range.
  • the absorbance is preferably 0.001 or more, more preferably 0.002 or more, still more preferably 0.01 or more, and particularly preferably 0.03 or more.
  • 0.05 or more is very preferable, 0.08 or more is very preferable, 0.09 or more is still more preferable, 0.1 or more is further preferable, and 0.2 or more is particularly preferable.
  • the absorbance is preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.3 or less, and particularly preferably 0.25 or less. 0.22 or less is very preferable. From the above viewpoint, the absorbance is more preferably more than 0 and 0.5 or less. The absorbance can be adjusted by adjusting the content of free particles in the abrasive grains.
  • the absorbance can be reduced by reducing the number of revolutions in stirring the liquid containing the first particles and the second particles, weakening the electrostatic repulsion generated between the particles, and the like.
  • an abrasive having an absorbance of 0 for light having a wavelength of 380 nm in a liquid phase obtained when the slurry is centrifuged may be used.
  • Such abrasive grains can be obtained by removing free particles by centrifugation.
  • the light transmittance for light having a wavelength of 500 nm is preferably 50% / cm or more, more preferably 60% / cm or more, still more preferably 70% / cm or more, and 80% / cm. cm / cm or more, particularly preferably 90% / cm or more, and very preferably 92% / cm or more.
  • the upper limit of the light transmittance is 100% / cm.
  • the lower limit of the pH of the slurry according to the present embodiment is preferably 2.0 or more, more preferably 2.5 or more, and still more preferably 2.8 or more, from the viewpoint of further improving the polishing rate of silicon oxide containing carbon. 3.0 or more is particularly preferable, 3.2 or more is extremely preferable, 3.5 or more is very preferable, 4.0 or more is still more preferable, 4.2 or more is further preferable, and 4.3 or more is particularly preferable.
  • the upper limit of the pH is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.0 or less, particularly preferably 5.0 or less, from the viewpoint of further improving the storage stability of the slurry.
  • the pH is more preferably from 2.0 to 7.0.
  • the pH of the slurry is defined as the pH at a liquid temperature of 25 ° C.
  • the pH of the slurry can be adjusted by an acid component such as an inorganic acid and an organic acid; and an alkaline component such as ammonia, sodium hydroxide, tetramethylammonium hydroxide (TMAH), imidazole and alkanolamine.
  • a buffer may be added to stabilize the pH.
  • a buffer may be added as a buffer (a solution containing a buffer). Examples of such a buffer include an acetate buffer, a phthalate buffer and the like.
  • the pH of the slurry according to the present embodiment can be measured with a pH meter (for example, model number PHL-40 manufactured by Toa DKK Ltd.). Specifically, for example, after two-point calibration of a pH meter using a phthalate pH buffer (pH: 4.01) and a neutral phosphate pH buffer (pH: 6.86) as a standard buffer, The electrode of the pH meter is put in the slurry, and the value is measured after 2 minutes or more have passed and stabilized. The temperature of both the standard buffer and the slurry is 25 ° C.
  • the constituent components of the polishing liquid may be stored as a one-part polishing liquid, and a slurry (a first liquid) containing abrasive grains and a liquid medium, and an additive And an additive liquid (second liquid) containing a liquid medium, and the constituent components of the polishing liquid are separated into a slurry and an additive liquid so that the polishing liquid becomes the polishing liquid. It may be stored as a polishing liquid set.
  • the additive liquid may contain, for example, an oxidizing agent.
  • the constituents of the polishing liquid may be stored as a polishing liquid set divided into three or more liquids.
  • the slurry and the additive liquid are mixed immediately before or during polishing to prepare a polishing liquid.
  • the one-component polishing liquid may be stored as a polishing liquid storage liquid in which the content of the liquid medium is reduced, and may be used after being diluted with the liquid medium during polishing.
  • the plural-liquid type polishing liquid set may be stored as a storage liquid for slurry and a storage liquid for additive liquid in which the content of the liquid medium is reduced, and may be used after being diluted with the liquid medium during polishing.
  • the polishing method according to the present embodiment (such as a method for polishing a substrate) includes a polishing step of polishing a surface to be polished (such as a surface to be polished of a substrate) using the slurry.
  • the surface to be polished contains silicon oxide containing carbon.
  • the slurry in the polishing step may be a polishing liquid obtained by mixing the slurry in the polishing liquid set and the additive liquid.
  • the slurry is supplied between the material to be polished and the polishing pad while the material to be polished of the substrate having the material to be polished is pressed against a polishing pad (polishing cloth) of a polishing platen.
  • the substrate and the polishing platen are relatively moved to polish the surface to be polished of the material to be polished.
  • at least a part of the material to be polished is removed by polishing.
  • the substrate to be polished includes a substrate to be polished and the like.
  • the substrate to be polished include a substrate in which a material to be polished is formed on a substrate (for example, a semiconductor substrate on which an STI pattern, a gate pattern, a wiring pattern, and the like are formed) for manufacturing a semiconductor element.
  • silicon oxide containing carbon can be used as the material to be polished.
  • the material to be polished may be a single material or a plurality of materials. When a plurality of materials are exposed on the surface to be polished, they can be regarded as the materials to be polished.
  • the material to be polished may be in the form of a film (a film to be polished), or may be a silicon oxide film containing carbon or the like.
  • the material to be polished formed on such a substrate is polished with the slurry, and an excess portion is removed, thereby eliminating irregularities on the surface of the material to be polished and forming a smooth surface over the entire surface of the material to be polished. Obtainable.
  • a general polishing apparatus having a holder capable of holding a substrate having a surface to be polished and a polishing platen to which a polishing pad can be attached can be used as the polishing apparatus.
  • Each of the holder and the polishing table is provided with a motor or the like whose rotation speed can be changed.
  • a polishing apparatus for example, a polishing apparatus: F-REX300 manufactured by Ebara Corporation or a polishing apparatus: MIRRA manufactured by APPLIED @ MATERIALS can be used.
  • polishing pad a general nonwoven fabric, foam, non-foam, or the like can be used.
  • material of the polishing pad include polyurethane, acrylic resin, polyester, acrylic-ester copolymer, polytetrafluoroethylene, polypropylene, polyethylene, poly4-methylpentene, cellulose, cellulose ester, polyamide (eg, nylon (trade name)) And aramid), polyimide, polyimide amide, polysiloxane copolymer, oxirane compound, phenol resin, polystyrene, polycarbonate, epoxy resin and the like.
  • the material of the polishing pad is preferably at least one selected from the group consisting of foamed polyurethane and non-foamed polyurethane, particularly from the viewpoint of further improving the polishing rate and flatness.
  • the polishing pad is preferably provided with a groove processing for accumulating slurry.
  • the surface to be polished containing silicon oxide containing carbon can be polished.
  • the present embodiment can be suitably used for forming an STI and for high-speed polishing of an interlayer insulating material.
  • the lower limit of the polishing rate of silicon oxide containing carbon is preferably 50 nm / min or more, more preferably 100 nm / min or more, further preferably 120 nm / min or more, and particularly preferably 150 nm / min or more.
  • This embodiment can also be used for polishing a premetal insulating material.
  • the premetal insulating material include silicon oxide, phosphorus-silicate glass, boron-phosphorus-silicate glass, silicon oxyfluoride, and amorphous carbon fluoride.
  • This embodiment can be applied to insulating materials other than silicon oxide containing carbon.
  • insulating materials include high dielectric constant materials such as Hf-based, Ti-based, and Ta-based oxides; semiconductor materials such as silicon, amorphous silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, and organic semiconductors; and GeSbTe. Phase change materials; inorganic conductive materials such as ITO; and polymer resin materials such as polyimide, polybenzoxazole, acrylic, epoxy, and phenol.
  • the present embodiment is applicable not only to a film-shaped polishing target but also to various substrates made of glass, silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, sapphire, plastic, or the like.
  • This embodiment is applicable not only to the manufacture of semiconductor elements, but also to image display devices such as TFTs and organic ELs; optical components such as photomasks, lenses, prisms, optical fibers, and single-crystal scintillators; optical devices such as optical switching elements and optical waveguides.
  • a light-emitting element such as a solid-state laser or a blue laser LED; and a light-emitting element such as a magnetic disk or a magnetic head.
  • a method for producing abrasive grains including a step of bringing first particles containing a cerium oxide into contact with second particles containing a cerium compound.
  • a slurry manufacturing method including a step of obtaining abrasive grains by the abrasive grain manufacturing method.
  • cerium oxide particles Particles containing cerium oxide (first particles; hereinafter, referred to as “cerium oxide particles”) mixed with ammonium dihydrogen phosphate (molecular weight: 97.99) manufactured by Wako Pure Chemical Industries, Ltd.
  • a cerium oxide slurry (pH: 7) containing 5.0% by mass (solid content) of cerium oxide particles was prepared.
  • the amount of ammonium dihydrogen phosphate was adjusted to 1% by mass based on the total amount of cerium oxide particles.
  • cerium oxide slurry An appropriate amount of cerium oxide slurry was charged into Beckman Coulter Co., Ltd. trade name: DelsaNano @ C, and the measurement was performed twice at 25 ° C. The average value of the indicated zeta potential was obtained as the zeta potential.
  • the zeta potential of the cerium oxide particles in the cerium oxide slurry was -55 mV.
  • the obtained precipitate (precipitate containing cerium hydroxide) was centrifuged (4000 min -1 , 5 minutes), and then the liquid phase was removed by decantation to perform solid-liquid separation. After mixing 10 g of the particles obtained by the solid-liquid separation and 990 g of water, the particles are dispersed in water using an ultrasonic cleaner, and the particles containing cerium hydroxide (second particles; hereinafter, referred to as “second particles”). A cerium hydroxide slurry containing “cerium hydroxide particles” (particle content: 1.0% by mass) was prepared.
  • the average particle size (average secondary particle size) of the cerium hydroxide particles in the cerium hydroxide slurry was measured using a trade name: N5 manufactured by Beckman Coulter KK and found to be 10 nm.
  • the measuring method is as follows. First, about 1 mL of a measurement sample (cerium hydroxide slurry; aqueous dispersion) containing 1.0% by mass of cerium hydroxide particles was placed in a 1 cm square cell, and then the cell was placed in N5.
  • the refractive index of the measurement sample information of N5 software was set to 1.333, the viscosity was set to 0.887 mPa ⁇ s, the measurement was performed at 25 ° C., and the value indicated as Unimodal Size Mean was read.
  • the cerium hydroxide particles at least partially contained particles having nitrate ions bonded to the cerium element. Further, since the particles having hydroxide ions bonded to the cerium element are contained in at least a part of the cerium hydroxide particles, it was confirmed that the cerium hydroxide particles contained cerium hydroxide. From these results, it was confirmed that the cerium hydroxide contained hydroxide ions bonded to the cerium element.
  • cerium hydroxide slurry (particle content: 1.0% by mass) was placed in a 1 cm square cell, and the cell was placed in a spectrophotometer (device name: U3310) manufactured by Hitachi, Ltd.
  • the absorbance was measured in the wavelength range of 200 to 600 nm, and the absorbance for light having a wavelength of 400 nm and the light transmittance for light having a wavelength of 500 nm were measured.
  • the absorbance for light having a wavelength of 400 nm was 2.25, and the light transmittance for light having a wavelength of 500 nm was 92% / cm.
  • Example 1 20 g of the cerium hydroxide slurry and 1940 g of ion-exchanged water were mixed while stirring at a rotation speed of 300 rpm using two stirring blades to obtain a mixed solution. Subsequently, 40 g of the cerium oxide slurry was mixed with the mixed solution while stirring the mixed solution, and the mixture was irradiated with ultrasonic waves using an ultrasonic cleaning machine (device name: US-105) manufactured by SND Corporation. While stirring.
  • an ultrasonic cleaning machine device name: US-105
  • cerium hydroxide particles not in contact with the cerium oxide particles (A content of cerium oxide particles: 0.1% by mass, a content of cerium hydroxide particles: 0.01% by mass, pH: 4.1) was prepared.
  • the pH of the test slurry was measured using a model number PHL-40 manufactured by Toa DKK Corporation (the same applies hereinafter).
  • Example 2 While stirring at a rotation speed of 300 rpm using a two-blade stirring blade, 30 g of the cerium hydroxide slurry and 1930 g of ion-exchanged water were mixed to obtain a mixed solution. Subsequently, 40 g of the cerium oxide slurry was mixed with the mixture while stirring the mixture, and the mixture was irradiated with ultrasonic waves using an ultrasonic cleaning machine (device name: US-105) manufactured by SND Corporation. While stirring.
  • an ultrasonic cleaning machine device name: US-105
  • cerium hydroxide particles not in contact with the cerium oxide particles (A content of cerium oxide particles: 0.1% by mass, a content of cerium hydroxide particles: 0.015% by mass, pH: 3.9) was prepared.
  • Example 3 30 g of the cerium hydroxide slurry, 50 g of ion-exchanged water, and 20 g of the cerium oxide slurry were sequentially added to a cylindrical container containing zirconia beads having a diameter of 1 mm to obtain a mixed solution. Subsequently, the mixture was placed on a mix rotor (device name: MR-5) manufactured by AS ONE Corporation and stirred at 100 rpm. After that, 900 g of ion-exchanged water was added, followed by stirring.
  • MR-5 mix rotor manufactured by AS ONE Corporation
  • cerium hydroxide particles not in contact with the cerium oxide particles (A content of cerium oxide particles: 0.1% by mass, a content of cerium hydroxide particles: 0.03% by mass, pH: 4.4) was prepared.
  • zeta potential of abrasive grains An appropriate amount of test slurry was put into a trade name “DelsaNano C” manufactured by Beckman Coulter, Inc. The measurement was performed twice at 25 ° C., and the average value of the displayed zeta potential was adopted.
  • the zeta potential of Examples 1 to 3 was +55 mV
  • the zeta potential of Comparative Example 1 was -55 mV
  • the zeta potential of Comparative Example 2 was +50 mV
  • the zeta potential of Comparative Example 3 was -35 mV.
  • a test solution was prepared by adjusting the content (total amount of particles) of abrasive grains in the test slurry (excluding Comparative Example 3) to 0.1% by mass (diluted with ion-exchanged water). 7.5 g of the test solution is placed in a centrifuge (trade name: Optima MAX-TL) manufactured by Beckman Coulter, Inc., and treated at a centrifugal acceleration of 5.8 ⁇ 10 4 G at a set temperature of 25 ° C. for 5 minutes to obtain a supernatant. I got
  • ⁇ CMP evaluation> The content of abrasive grains (total amount of particles) in the test slurry was adjusted to 0.1% by mass (diluted with ion-exchanged water) to obtain a CMP polishing liquid.
  • the substrate to be polished was polished under the following polishing conditions using the CMP polishing liquid.
  • the values of the zeta potential, the average particle diameter of the abrasive grains, and the pH in the CMP polishing liquid were equivalent to the values of the test slurry described above.
  • Polishing device MIRRA3400 (manufactured by APPLIED MATERIALS) Flow rate of CMP polishing liquid: 250 mL / min Substrate to be Polished: As a blanket wafer on which no pattern was formed, a substrate to be polished having a black diamond film (BD film, manufactured by Applied Materials) having a thickness of 2 ⁇ m formed on a silicon substrate by a plasma CVD method was used.
  • BD film black diamond film, manufactured by Applied Materials

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  • General Physics & Mathematics (AREA)
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Abstract

L'invention concerne une suspension épaisse pour polir un oxyde de silicium contenant du carbone, la suspension épaisse contenant des grains abrasifs et un milieu liquide, les grains abrasifs contenant une première particule et une seconde particule en contact avec la première particule, la seconde particule présentant un diamètre de particule plus petit qu'un diamètre de particule de la première particule, la première particule contenant de l'oxyde de cérium, et la seconde particule contenant un composé de cérium.
PCT/JP2018/035445 2018-09-25 2018-09-25 Suspension épaisse et procédé de polissage WO2020065723A1 (fr)

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PCT/JP2018/035445 WO2020065723A1 (fr) 2018-09-25 2018-09-25 Suspension épaisse et procédé de polissage
CN201880097934.8A CN112740366A (zh) 2018-09-25 2018-09-25 浆料及研磨方法
KR1020217010330A KR102382508B1 (ko) 2018-09-25 2018-09-25 슬러리 및 연마 방법
US17/278,974 US20220033680A1 (en) 2018-09-25 2018-09-25 Slurry and polishing method
JP2020547634A JP6888744B2 (ja) 2018-09-25 2018-09-25 スラリ及び研磨方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7373026B2 (ja) 2021-07-08 2023-11-01 エスケー エンパルス カンパニー リミテッド 半導体工程用研磨組成物及びそれを用いた研磨された物品の製造方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020021680A1 (fr) * 2018-07-26 2020-01-30 日立化成株式会社 Suspension et procédé de polissage

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011054906A (ja) * 2009-09-04 2011-03-17 Hitachi Chem Co Ltd スラリーの保存方法及び保存容器
JP2012238831A (ja) * 2011-01-25 2012-12-06 Hitachi Chem Co Ltd Ｃｍｐ研磨液及びその製造方法、複合粒子の製造方法、並びに基体の研磨方法
WO2013125445A1 (fr) * 2012-02-21 2013-08-29 日立化成株式会社 Abrasif, ensemble abrasif et procédé d'abrasion d'un substrat
JP2017110177A (ja) * 2015-12-14 2017-06-22 日立化成株式会社 研磨液、研磨液セット及び基体の研磨方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3278532B2 (ja) 1994-07-08 2002-04-30 株式会社東芝 半導体装置の製造方法
JPH10106994A (ja) 1997-01-28 1998-04-24 Hitachi Chem Co Ltd 酸化セリウム研磨剤及び基板の研磨法
CN1746255B (zh) 2001-02-20 2010-11-10 日立化成工业株式会社 抛光剂及基片的抛光方法
JP2006249129A (ja) 2005-03-08 2006-09-21 Hitachi Chem Co Ltd 研磨剤の製造方法及び研磨剤
JP5287174B2 (ja) * 2008-04-30 2013-09-11 日立化成株式会社 研磨剤及び研磨方法
KR101075491B1 (ko) * 2009-01-16 2011-10-21 주식회사 하이닉스반도체 반도체 소자의 제조방법
CN103374330B (zh) 2010-11-22 2015-10-14 日立化成株式会社 磨粒的制造方法、悬浮液的制造方法以及研磨液的制造方法
CN103409108B (zh) * 2010-11-22 2015-04-22 日立化成株式会社 悬浮液、研磨液套剂、研磨液、基板的研磨方法及基板
CN103500706A (zh) 2010-11-22 2014-01-08 日立化成株式会社 悬浮液、研磨液套剂、研磨液、基板的研磨方法及基板
JP2014099581A (ja) * 2012-04-27 2014-05-29 Hitachi Chemical Co Ltd スラリー、研磨液セット、研磨液、基体の研磨方法及び基体
WO2013175856A1 (fr) * 2012-05-22 2013-11-28 日立化成株式会社 Bouillie, ensemble de solution de polissage, solution de polissage, procédé de polissage de substrat, et substrat
US20170194160A1 (en) * 2016-01-06 2017-07-06 Cabot Microelectronics Corporation Method of polishing a low-k substrate
SG11201908858SA (en) * 2017-03-27 2019-10-30 Hitachi Chemical Co Ltd Slurry and polishing method
WO2020021680A1 (fr) * 2018-07-26 2020-01-30 日立化成株式会社 Suspension et procédé de polissage
WO2019182061A1 (fr) * 2018-03-22 2019-09-26 日立化成株式会社 Liquide de polissage, ensemble liquide de polissage et procédé de polissage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011054906A (ja) * 2009-09-04 2011-03-17 Hitachi Chem Co Ltd スラリーの保存方法及び保存容器
JP2012238831A (ja) * 2011-01-25 2012-12-06 Hitachi Chem Co Ltd Ｃｍｐ研磨液及びその製造方法、複合粒子の製造方法、並びに基体の研磨方法
WO2013125445A1 (fr) * 2012-02-21 2013-08-29 日立化成株式会社 Abrasif, ensemble abrasif et procédé d'abrasion d'un substrat
JP2017110177A (ja) * 2015-12-14 2017-06-22 日立化成株式会社 研磨液、研磨液セット及び基体の研磨方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7373026B2 (ja) 2021-07-08 2023-11-01 エスケー エンパルス カンパニー リミテッド 半導体工程用研磨組成物及びそれを用いた研磨された物品の製造方法

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